DE1793710A1 - Process for the production of epoxy compounds - Google Patents

Description

Case 650-1D2

Patent attorneys

i, 38

FIRMENICH & CIE , Geneva (Switzerland)

Process for making epoxy compounds

The invention relates to new epoxy compounds the formula

Ia, b

and their manufacturing process. ·

The dashed lines each represent a double bond.

'According to the invention, the epoxies Ia and Ib by epoxidation of the non-conjugated double bond of ocimen or myrcene using a peracid in a buffered medium,

The ocimen contains the dotted line dargeotellr-e -... double bond in the main carbon chain , while

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the myrcene that represented by a dashed line _; Double bond, contains in the side chain. In the case of substances with an ocime structure, the configuration shown in the structural formula above is trans. The compounds which have an ocimene structure can of course also show themselves in the form of their cis isomers. The peracid used for the epoxidation can be, for example, peracetic acid, perbenzoic acid, monochloroperbenzoic acid or perphthalic acid. Chlorinated hydrocarbons, for example chloroform, methylene chloride, trichlorethylene or dichloroethane, can be used as solvents. The use of peracetic acid in methylene chloride is advantageous. Organic alkali salts such as sodium or potassium formate, acetate, propionate, butyrate, oxalate, citrate or tartrate are suitable as buffer substances. Sodium acetate is advantageously used.

The selective epoxidation of the non-conjugated Double bond of ocimene or myrcene while avoiding attack on the other double bonds is a critical one Operation and must be performed under carefully controlled conditions if good yields of the desired Pero.xyds are to be achieved. For example, it was found that the regulation of the reaction temperature according to the usual method ;; is insufficient. The cooling capacity of the temperature control device (Cooling apparatus) should be dimensioned in such a way that after the addition of the epoxidation agent has been started with a

., ZM 9 8 A 3/1 1 2 9 BAD

the temperature quickly increases to a certain speed certain level increases and remains practically constant until the addition of the epoxidation agent is complete. To achieve optimal yields, it is useful, for example, that Cool the reaction vessel to about 0 ° C and add the epoxidizing agent to add drop by drop at such a rate, that the temperature rises first to 20-25 C and then remains practically constant at this level without the cooling device having to be put out of operation.

The monoepoxides of eis-Ocimen and trans-Ocimen are fragrances that have interesting olfactory properties. They are particularly suitable for enhancing the top note of perfume compositions and are expediently used in amounts of about 0.5 to 3 %, based on the total weight of a perfume composition. However, these figures should not be interpreted as limit values, since the epoxides mentioned can also be used in higher quantities, depending on the desired odor effects.

The monoepoxides of cis-Ocimen and trans-Ocimen are also interesting starting compounds for the production of α- and ß-Sinensal (sesquiterpene aldehydes _a in an orange variety,. Citrus sinensis / "see J. Org. Chem. J50, '1690 (1965 ) 7 have been found), according to the method illustrated in the following diagram:

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Peracid

Opening of the epoxy ring

Ocimen
(Myrcene) 1. Epoxies
la 2. CH-CH ₂ -CH = NR Hydrolysis / H ⁺ CHO ■ 'S

sec-ocimenol (sec-myrcenol)

CHO

α- and ß-Sinensal

The dashed lines each represent a double bond. The ocimen contains the one indicated by a dashed line Line shown double bond in the main carbon chain, while the myrcene that shown by a dashed line Contains double bond in the side chain. In the case of substances with an ocimene structure, the reaction chart above is Configuration shown trans. However, the same scheme also applies to substances with an 'eis configuration in the ocimene structure. - - ·

The following examples in which the temperatures are given in degrees Celsius, show how the invention can be carried out * -

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example Production of trans-epoxyocimes Epoxidation of trans-oils

A solution of 204 g of trans-Ocimen and 150 g of sodium acetate in 750 ml of methylene chloride was at for 1 hour Stirred at room temperature and then cooled to 0 within about 15 minutes. Then a solution of 3 g Sodium acetate in 315 g of 42% peracetic acid dropwise entered at such a rate that the temperature of the reaction mixture rose to 20-25 °. By Maintaining a suitable rate of addition, but without removing the cooling device, was the temperature held constant until the addition of the peracetic acid was complete. The addition of the peracetic acid took time under these conditions

about 1 hour. The reaction equipment was stirred for a further 4 hours at room temperature, whereupon the solid by-product was filtered off and washed with methylene chloride. The combined methylene chloride solutions were poured into ice water, the mixture was shaken vigorously and the organic layer was separated. The latter was washed with 125 ml portions of the following solvents: water (once), saturated sodium bicarbonate solution (twice) and water (once). After drying and concentration, the residue was distilled. 205 g of trans-epoxyocimes were obtained (90 $ yield), b.p. = 45-47 ° / 0.1 Torr, df " = 0.9082jn ^ = 1.4802.

2098 A3 / 1129

example Manufacture of cis-ocine epoxide

cis-Ocimen was epoxidized in the manner described in Example 1 for trans-Ocimen. The cis-ocimenepoxide had the following constants: djjj ⁰ = 0.8996; n ^ ° = the yield was about 90 %.

B ice pie I 3

Manufacture of epoxymyrcene Epoxidation of myrcene

Freshly distilled technical myrcene (204 g), which contained about 10 % limonene, was epoxidized in the manner described in Example 1. 205 g of epoxymyrcene (90 % yield) were obtained. Bp = 41-44 ° / O, 06 Torr. Analysis :

for C ₁₀ H ₁₆ OC 78.89 %, H 10.59 %, found C 78.65 %, H 10.40 %.

n ^ ° = 1.4632; djj ° = 0.8865; f «/ ^ ⁰ = -3.95 °.

example ¹ y

A perfume composition with a scent of lavender was prepared by mixing the following components:

Components parts by weight

Lavender Essence 515

Rosemary essence 20

Sage essence 30

Bergamot Essence 90

Lemon Essence 40

Geranium Bourbon 40

Nonanal, 1 % * 10 undecanal, 1 % *, 20

209843/1129

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793710

Dodecanal, IS *

Methyl phenyl ketone., 10 % * 5

Phenylethyl alcohol HO

Acetic acid citronelly ester 10 Curaarin "50

Ambrette Musk '10

Ketone Mosehus 30

Lavender absolutely MQ

Oak moss absolutely 5

Pentadeeanolld 25

985 * in phthalic acid diethyl ester

By adding 15 parts by weight of trans-epoxyocimen the top note for this raw material composition became significantly strengthened and improved,

Example 5 '

The present example describes the preparation of aie oc - and beta-sinensal.

A. 40 g of trans-Epoxyoeifflen were a solution of 8 g of p-toluenesulfonic acid and 2 g of hydroquinone in 800 ml Benzene added, whereupon the reaction mixture during Was stirred for 8 hours at 25-30 °. The reaction mixture 160 ml of 256-strength Fatrolauge was then added and stirred vigorously for 1 hour. The organic Layer was separated, washed twice with water, dried over sodium sulfate, concentrated in vacuo and distilled over 2 g of solid sodium carbonate. 25 g (60%) of pure trans-sec-ocimenol were obtained / 2,6-dimethyl-octatriene- (2,5,7) -ol- (317, bp = 45-47 ° / 0.001 Torr, n ^ ° = 1.4983, d | ° «0.9083.

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75 g of trans-Epoxyocimen were added dropwise at -5 to 0 ° in 500 ml of 50 ^ aqueous sulfuric acid. The reaction mixture was stirred vigorously for 1 hour while slowly increasing the temperature 20-25 °. The reaction mixture was with Extracted methylene chloride, whereupon the extract several times with water, then with saturated aqueous sodium carbonate solution and finally washed with water. The extract was dried, concentrated and distilled. Secondary trans-ocimenol was obtained in a yield of $ 70-80.

A mixture of 50 g of trans-sec-ocimenol, 300 g of vinyl ethyl ether, 5 g of mercuric acetate and 10 g of sodium acetate was stirred for 40 hours under nitrogen at reflux temperature. After cooling, the reaction mixture was filtered and washed with 300 ml of water. The excess vinyl ethyl ether was evaporated, whereupon the residue was diluted with 200 ml of xylene. The solution was heated at 150 ° for 1 hour, after which the xylene was evaporated under reduced pressure. Distillation of the residue gave 35 g (60 $) of trans-4,8-dimethyl-8-vinyl-nonadiene- (4,7) -al, b.p. = 40-60 ^O / 0.04 Torr. As the chromatographic analysis showed, this product contained about 30 $ sec-ocimenol, which, however, had no disruptive influence on the conversion of the aldehyde into ÖC-Sinensal ... 20984 3/1129

and recovered from the final reaction stage.

350 mg of crushed lithium metal was suspended in 12 ml of dry ether under nitrogen. The suspension was cooled to -20 ° and a solution of 3 »84 g of methyl iodide (27 millimoles) in 8 ml of ether was added dropwise. After the temperature had risen to 0 °, the reaction mixture was stirred for a further hour and then a solution of 2.13 g of diisopropylamine (21 millimoles) in 20 ml of ether was added dropwise at 0 °. The reaction mixture was stirred for 45 minutes at 0 °, then over the course of 20 minutes with a solution of 2.83 g of propylidene-tert-butylimine (25 millimoles) in 20 ml of ether and finally after further stirring for 20 minutes at 0 ° within 20 minutes Minutes at -60 ° with a solution of 3 _} 71 g of trans-4,8-dimethyl-8-vinyl-nonadien- (4,7) -al (21 millimoles) added dropwise. While the reaction mixture was stirred for a further hour, the temperature was allowed to rise to room temperature. The reaction mixture was poured into a solution of 10 g of oxalic acid in 150 ml of ice water and stirred for 30 minutes, whereupon the organic layer was separated off and the aqueous layer was extracted with ether. The combined extracts were washed, dried and finally subjected to a fractional distillation. 2 "73 g"'-Sinensal were obtained, b.p. = 115-120 ° / 0.1 Torr. IR spectrum

(CHCl3,): 1725, 1650, 1610, 995, 895 cnT ¹ ; BMR- (CClJ:. 2 0984371129

9.65 ppm (1 H, s), 6.35 ppm (1 H, t, J = 6 cps), 6.29 ppm (1 H, d of d, j = 10 and 10 cps), 4.85 ppm (4 H), 2.8? ppm (2 H, t, J = 7 cps), 1.9-2.6 ppm (4 H), 1.72 "ppm (9 H).

B. A solution, cooled to -10 °, of 126.5 g (1.25 mol) of diisopropylamine in 500 ml of cyelohexane was added dropwise to 465 g of a 155% strength solution of butyllithium in hexane within 20 minutes with vigorous stirring and under nitrogen. The reaction mixture was stirred for a further 10 minutes at 0 °, whereupon it was cooled to -5 ° and 76 g (0.5 mol) of epoxymyrcene were added dropwise within 10 minutes. The temperature was then allowed to rise slowly to 25 ° and kept constant at this level for 11/2 hours. The reaction mixture was poured into ice water, whereupon the organic layer was separated off, first with 10 # aqueous hydrochloric acid and then with water The individual wash waters were extracted with petroleum ether (250 ml), whereupon the extracts were combined, concentrated and distilled to give 53 g (69.8 $) of sec-myrcenol with a boiling point of 47 ° / 0 .04 torr.
Analysis:

for C ₁₀ H ₁₆ OC $ 78.89> H 10.59 # found C 78.61 56 H 10.37 #.

n £ ° _e . 1.4890; d | ° = 0.8986;
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A solution of 126.5 g of biisopropylamine in 500 ml Cyelohexane was added dropwise at -1.0 ° under nitrogen in 465 g of an approximately 15 # solution of butyllithium added in hexane. Then were with good stirring "at From -5 ° to 0 °, 76 g of epoxymyreen were added dropwise. The reaction mixture was then mixed with 200 ml of ice water stirred and neutralized with dilute hydrochloric acid. By working up in the previous one Paragraph described ¥ ice was sec.-Jiyrcenol in about ^ obtained the same yield.

A mixture of 50 g sec-myrcenol, 300 g n-butyl vinyl ether, 1 g of mercury acetate and 10 g of sodium acetate was for 40 hours under nitrogen at reflux temperature (120 °) heated. During this time, 1 g of additional mercuric acetate was added every 6 hours. The reaction flask was connected to a descending condenser and the excess n-butyl vinyl ether distilled off at ordinary pressure. By Destil- ^ Lation of the residue under reduced pressure was in a yield of 75S ^ 4t8-Diinethyl-8-vinyl-nonadien- (4 »8) -al get that still about I55S un-implemented Contained alcohol. This alcohol could be recovered when the aldehyde was converted into p-sinensal.

A 600 ml abs. Ether and 64O g of a 1555 Containing solution of butyllithium (1.5 mol) in hexane Solution was cooled to -10 °. This solution was within

_ 209843/1129

1 hour under nitrogen and with stirring a solution of 128 g of diisopropylamine (1.265 mol) in 600 ml of abs. Aether added. The temperature was allowed to rise to 0 ° and the reaction mixture was stirred for a further 1/2 hour. After cooling the reaction mixture to -10 ° , a solution of 208 g of propylidene-cyclohexylimine (1.5 mol, ep. = 56-58 ° / 15 torr) in 600 ml of ether was added dropwise to it within 1 hour. The reaction mixture was stirred for 1 hour at 0 °, then cooled to -65 ° and finally within 1/2 hour at a temperature of -66 ° to -62 ° with a solution of 225 g of 4,8-dimethyl-8-vinyl -nonaäien- (4.8) -al (1.265 mol) added to 600 ml of ether. The temperature of the reaction mixture was allowed to rise to 25 ° (within 1 hour), whereupon the reaction mixture was poured into a solution of 600 g of oxalic acid in 8 liters of water while stirring at 0 °. The organic layer was separated off and the aqueous phase was extracted twice with ether (2 liters). Me extracts were washed first with 5% aqueous sodium bicarbonate solution and then with water. By drying and concentrating the extracts, raw / 3-sinensal was obtained in a yield of 70%, boiling point = 100-111 ° / 0.04 torr. For analytical purposes, a sample of silica was chromatographed using a 3% solution of ethyl acetate in hexane as the eluent. The purified product had a

from 88-89%), 02 Torr. IR spectrum (OHCl-): 3090, 209843/1129

2710, 1800, 1680, 1640, 1590, 995, 905 cm " ^1. UV spectrum (ethanol): 2260 £ (£, = 34000). NMR spectrum (GCl ₄ ): 9.33 ppm (1 H, s ), 6.37 ppm (1 H, t, J = 6 cps), 6.30 ppm (1 E, d of d, J = 17 and 10 cps), 4.8-5.4 ppm (5H ₁ m ), 1.9-2.6 ppm (8 H, mj, 1.69 ppm (3 H, s wide), 1.61 ppm (3 H, s "wide).
Analysis;

calculated for C ₁₅ H ₂₂ O 0 82.51 % H 10.16 %

found C 82.58 # H 10.39 ^. φ

The dinitrophenylhydrazone from jS-Sinensal melted at 86-88 ⁰ 5,

2 0 9843/1 129

Claims (6)

J cis-epoxyocimes. 2. trans-epoxyocimes. 3. Process for the preparation of epoxy compounds the formula Ia, b characterized in that one has the non-conjugated double bond epoxidized by ocimen or hyrcene by means of a peracid in a buffered medium. 4. The method according to claim 3, characterized in that that the epoxidation by means of peracetic acid in the presence, of sodium acetate in a chlorinated solvent such as chloroform or methylene chloride. 5. The method according to claim 3 and 4, characterized in that the epoxidation is carried out by cooling the epoxidizing solution to about 0 ⁰ C and adding the epoxidizing agent at such a rate that the temperature rises to 20-25 ° C and on this height 'remains constant without the cooling being interrupted. 6. Fragrance composition containing a compound according to Claim 1 and / or 2. 209843 ^ uurx-BU- * BAD ORiGiNAL